Matériaux multiferroïques ont suscité beaucoup d'intérêt au cours des dernières années. Notre étude est consacrée à un système prototype: manganite d'yttrium. En particulier, nous nous concentrons sur les propriétés ferroélectriques sous forme massive monocristalline et sous forme de couches minces. Manganite d'yttrium appartient à la classe des composés ABO3. La plupart des études théoriques de la ferroélectricité à ce jour se sont concentrées sur perovskite cubique ABO3. Manganite d'yttrium est hexagonale et est un ferroélectrique impropre. Nous nous sommes intéressés à étudier théoriquement et expérimentalement comment ces deux fonctions se comportent sous forme de film mince. / Multiferroic materials have attracted much interest during the recent years. Our study is devoted to a prototypic system: yttrium manganite. In particular, we focus on the ferroelectric properties in bulk and in thin film form. Yttrium manganite belongs to the class of ABO3 compounds. Most theoretical studies of ferroelectricity to date were concentrated on cubic perovskite ABO3. Yttrium manganite is hexagonal and is an improper ferroelectric. We were interested to study theoretically and experimentally how these two features behave in thin film form.

Les concepts de matériaux multiferroïques et/ou magnétoélectriques permettent d’envisager de nouveaux dispositifs de mémoires plus performants et moins consommateurs d’énergie. Malheureusement de tels matériaux présentant ces propriétés à température ambiante ne sont pour l’instant pas disponibles. Les matériaux qui font l’objet des études présentées dans ce manuscrit, les ferrites de gallium Ga2-xFexO3, 0,7 ≤ x ≤ 1,4, sont d’excellents candidats. Le présent travail de thèse en a étudié les propriétés électriques, tant sur matériaux massifs que couches minces. Nous avons mesuré une polarisation sur composés massifs du même ordre de grandeur que celle précédemment déterminée par calculs ab initio. Une considérable réduction des courants de fuite habituellement observés en couches minces a été possible grâce à la substitution de Fe2+ par Mg2+. Une polarisation réversible et un effet magnétoélectrique ont alors pu être mis en évidence. Compte tenu du caractère ferrimagnétique à température ambiante des couches minces considérées, ceci constitue la première manifestation d’un matériau multiferroïque et magnétoélectrique à réel intérêt applicatif. / Concepts of multiferroic and magnetoelectric materials allow designing new memory devices with better performances and less energy consumption. Unfortunately, such materials with room temperature applicability are not yet available.The material concerned by this study, gallium ferrites Ga2-xFexO3, 0.7 ≤ x ≤ 1.4, are excellent candidates for such applications. This work aimed at studying the electrical properties of the bulk material, as well as in thin films. We have measured a polarization on the bulk samples comparable to the value estimated by first principle calculations. A considerable reduction of the leakage currents usually observed in oxide thin films has been achieved by the doping by substitution of Fe2+ in the structure, using Mg2+. A switchable polarization and a magnetoelectric effect at room temperature in thin films have been observed. Considering the room temperature ferrimagnetic behavior of this compound, this is the first manifestation of a multiferroic and magnetoelectric with real potential and technological applications.

L'avenir de la spintronique repose sur le développement de matériaux ayant des propriétés magnétiques remarquables. L'objectif de cette thèse est de comprendre la physique des deux matériaux fonctionnels proposés pour des applications spintroniques qui utilisent des simulations de la densité fonctionnelle.Nous nous sommes intéressés dans une première partie au ferrite de gallium pour lequel il a été montré que les propriétés dépendaient de la concentration de fer.Les spectres optiques ont été calculés et comparés aux spectres expérimentaux suggérant des niveaux élevés de désordre. Dans la deuxième partie, nous avons montré une polarisation de spin à l’interface hybride formée entre la phthalocyanine de manganèse et la surface de cobalt,en accord avec les expériences de photoémission.La formation de la spinterface a été expliquée par différents mécanismes d'hybridation dans chaque canal de spin.Cette polarisation de spin est coordonnée avec des moments magnétiques induits sur les sites moléculaires. / The future of the spintronics technology requires developing functional materials with remarkable magnetic properties. The aim of this thesis is to understand the physics of functional materials proposed for spintronic applications using ab-initio density functional simulations. We investigated the properties of two different functional materials. We first studied the magnetoelectric gallium ferrite GFO. The dependence of the different properties on the iron concentration has been demonstrated and discussed. The optical spectra were calculated and compared to the experimental once suggesting high levels of iron disorder. In the second part, we demonstrated a highly spin polarized hybrid interface formed between manganese phthalocyanine and cobalt surface in agreement with photoemission experiments. The formation of this spinterface was described by different hybridization mechanisms in each spin channel. This high spin polarization is coordinated with induced magnetic moments on the molecular sites.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / FundaÃÃo de Amparo à Pesquisa e ao Desenvolvimento CientÃfico e TecnolÃgico do MaranhÃo / CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Perovskitas duplas com fÃrmula na forma A2BBâO6 (A = La, Sr, Ca, B/Bâ = Co/Mn ou Fe/Mo) sÃo materiais multiferrÃicos de grande interesse na ciÃncia devido Ãs notÃveis propriedades, que permitem aplicaÃÃes em capacitores e em memÃrias, por exemplo. AlÃm disso, mudanÃas estruturais sÃo observadas entre a forma policristalina e o filme fino. Essas propriedades podem mudar de acordo com a rota utilizada para sintetizaÃÃo do material. No nosso trabalho estudamos filmes de La2CoMnO6 sintetizados pelo mÃtodo de Pechini Modificado (MPM), com trÃs deposiÃÃes e tratados em diferentes temperaturas: 700, 800 e 900 ÂC. Os filmes foram caracterizados por difraÃÃo de raios X, Microscopia EletrÃnica de Varredura (MEV), Microscopia de ForÃa AtÃmica e espectroscopia Raman à temperatura ambiente e tambÃm variando a temperatura. As tÃcnicas de MEV e AFM foram bastante eficientes na determinaÃÃo do diÃmetro mÃdio dos filmes, fornecendo resultados correspondentes. A tÃcnica de EDS trouxe dados qualitativos da composiÃÃo do material. A difraÃÃo de Raios X confirmou a fase do filme, alÃm de ter identificado a composiÃÃo do substrato: silÃcio e platina. A espectroscopia Raman em diversos pontos possibilitou identificar a regiÃo de melhor formaÃÃo do LCMO. O estudo da mudanÃa do fÃnon mais intenso com a temperatura mostrou diferentes temperaturas para a transiÃÃo de fase paramagnÃtica-ferromagnÃtica, possibilitando confirmar que a temperatura de calcinaÃÃo dos filmes determinou elevada desordem estrutural para os filmes de LCMO tratados a 700 e 900 ÂC. Discutimos nossos resultados com outros estudos na literatura, que mostram as medidas magnÃticas como um fator determinante para comprovar a temperatura do acoplamento spin-fÃnon.

Fundação de Apoio a Pesquisa e à Inovação Tecnológica do Estado de Sergipe - FAPITEC/SE / The RMnO3 (R=Y,Lu) compounds, members of the family of hexagonal manganites, are materials which exhibit strong magneto-electric coupling characteristic for multiferroic compounds. Despite the numerous studies with objective to reveal the origin of this phenomenon, the mechanism that is causing it is still not fully understood. The question that attracts special attention of scientific community is about the cause of ferroelectric distortion that occurs at certain temperatures in these materials. Although this issue is discussed in many papers, there is still no consensus what mechanism is responsible for it: (1) hybridization between the Mn dz2 orbital and O pz orbital (Mn d0 –ness model), (2) hybridization between the R dz2 orbital and O pz orbital (R d0 –ness model), (3) geometric effects or (4) charge transfer from Mn-O bonds to R-O bonds. Understanding of the mechanism that leads to ferroelectric polarization is necessary to speed application of these materials in ferroelectric memories or spintronics devices. Objective of the present work was to evaluate the first two possible mechanisms that might cause the ferroelectric distortion in RMnO3. Adopted strategy was to investigate what happens with the Mn-O and R-O chemical bonds after the structural phase transition from paraelectric to ferroelectric phase that occurs at high temperature, at which both phases are characterized by paramagnetic order of the Mn magnetic moments. For that purpose, the first-principles calculations based on density functional theory were carried on, with usage of the most modern exchange-correlation potentials. The chemical bonds were evaluated (1) qualitatively, by analysis of density of electronic states (DOS) and maps of electronic density along the bonds, and (2) quantitatively, in terms of topological analysis of Bader. The results revealed that no significant change occurred with Mn-O bonds, while the R-O bonds were affected by phase transition in the sense that R dz2 and O pz orbital exhibited enhanced hybridization in the ferroelectric phase. Therefore, the present study substantiates the R d0 –ness mechanism as the probable cause of ferroelectric distortions in RMnO3 compounds. / The RMnO3 (R=Y,Lu) compounds, members of the family of hexagonal manganites, are materials which exhibit strong magneto-electric coupling characteristic for multiferroic compounds. Despite the numerous studies with objective to reveal the origin of this phenomenon, the mechanism that is causing it is still not fully understood. The question that attracts special attention of scientific community is about the cause of ferroelectric distortion that occurs at certain temperatures in these materials. Although this issue is discussed in many papers, there is still no consensus what mechanism is responsible for it: (1) hybridization between the Mn dz2 orbital and O pz orbital (Mn d0 –ness model), (2) hybridization between the R dz2 orbital and O pz orbital (R d0 –ness model), (3) geometric effects or (4) charge transfer from Mn-O bonds to R-O bonds. Understanding of the mechanism that leads to ferroelectric polarization is necessary to speed application of these materials in ferroelectric memories or spintronics devices. Objective of the present work was to evaluate the first two possible mechanisms that might cause the ferroelectric distortion in RMnO3. Adopted strategy was to investigate what happens with the Mn-O and R-O chemical bonds after the structural phase transition from paraelectric to ferroelectric phase that occurs at high temperature, at which both phases are characterized by paramagnetic order of the Mn magnetic moments. For that purpose, the first-principles calculations based on density functional theory were carried on, with usage of the most modern exchange-correlation potentials. The chemical bonds were evaluated (1) qualitatively, by analysis of density of electronic states (DOS) and maps of electronic density along the bonds, and (2) quantitatively, in terms of topological analysis of Bader. The results revealed that no significant change occurred with Mn-O bonds, while the R-O bonds were affected by phase transition in the sense that R dz2 and O pz orbital exhibited enhanced hybridization in the ferroelectric phase. Therefore, the present study substantiates the R d0 –ness mechanism as the probable cause of ferroelectric distortions in RMnO3 compounds.

Made available in DSpace on 2016-08-18T18:44:20Z (GMT). No. of bitstreams: 1 Tese-RosivaldoXavierSilva.pdf: 12741226 bytes, checksum: 7bc7743bfa3e2f958b913f2d67969531 (MD5) Previous issue date: 2015-12-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The RE2CoMnO6 (RE = La e Y) and Gd(Co0.5Mn0.5)O3 samples were obtained via modified Pechini method (MPM). Raman spectroscopy (RS), Fourier transform infrared (FTIR) spectroscopy, X ray powder diffraction, X ray photoelectron spectroscopy (XPS), SQUID and scanning electron microscopy (SEM) were used to characterize the samples, investigate structural and microstructural evolution, as well as evaluate their vibrational, magnetic and intrinsic dielectric properties. The impact of synthesis conditions on the structural ordering was investigated. We obtained a good control of structural order depending on the annealing temperature for LCMO. We observed an increase in the saturation magnetization, lifetime of the phonons and dielectric constant while suppression of anti-site defects and reduction of dielectric loss. Our investigations on polar phonons by FTIR revealed the extrinsic character of CDC effect on LCMO and clarified the contributions of phonons for dielectric constant in these systems. The temperature dependence Raman spectra of GCMO was investigated between 40 and 300 K and revealed an intriguing spin-phonon coupling, characterized by an increase in the energy of the most intense stretching mode near the magnetic transítion. The correlation between the Raman data and the magnetization suggests that the structure influences the magnitude of the spin-phonon coupling. Correlated analysis of LCMO, GCMO and YCMO systems show that all samples have vibrational properties quite similar. The intrinsic dielectric constants were obtained from the polar phonons dispersive parameters ε intr ̴ 15.8, 17.9 and 16.0, making the contributions to this value explicit, as well as the quality factors, reciprocal of dielectric losses , 𝑄𝑢×𝑓 ≈ 124,74 e 83 THz, extrapolated to microwave region at 10 GHz, to LCMO, GCMO and YCMO, respectively. XPS measures showed that oxidation state for Co and Mn ions are similar each another, being mostly Co2 + and Mn4 + for all investigated systems, however to GCMO, the spin-phonon coupling behavior and losses relatively large indicate that this compound has a high level of structural disordering. / Amostras de RE2CoMnO6 (RE = La e Y) e Gd(Co0.5Mn0.5)O3 foram obtidas pelo método Pechini modificado (MPM). Espectroscopia Raman (RS), espectroscopia no infravermelho por transformada de Fourier (FTIR), difração de raios X (DRX), espectroscopia de fotoelétrons excitados por raios X (XPS), magnetometria e microscopia eletrônica de varredura (MEV) foram utilizados para caracterizar as amostras, investigar evolução estrutural e microestrutural bem como avaliar suas propriedades vibracionais, magnéticas e dielétricas intrínsecas. O efeito da temperatura de tratamento térmico sobre o ordenamento estrutural foi investigado. Um bom controle do ordenamento estrutural em função da temperatura de tratamento térmico para o La2CoMnO6 (LCMO) foi obtido. Observa-se um incremento da magnetização de saturação, aumento do tempo de vida dos fônons, supressão de defeitos de anti-sítio, redução de perdas dielétricas e incremento da constante dielétrica. A investigação dos fônons polares via FTIR revelaram o caráter extrínseco da constante dielétrica colossal (CDC) no LCMO e explicitou as contribuições dos fônons para a constante dielétrica nesses sistemas. A dependência dos espectros Raman com a temperatura do Gd(Co1/2Mn1/2)O3 (GCMO) foi investigada entre 40 e 300 K revelando um acoplamento spin-fônon, caracterizado pelo incremento na energia do modo de estiramento mais intenso próximo à transição magnética. A correlação entre os resultados obtidos pela espectroscopia Raman e a magnetização sugere que a ordem estrutural influencia a magnitude do acoplamento spin-fônon. Análise correlacionada dos sistemas LCMO, GCMO e YCMO, mostram que todas as amostras apresentam características vibracionais bastante semelhantes. A partir dos parâmetros de dispersão dos fônons polares foram obtidas as constantes dielétricas intrínsecas ε intr ̴ 15,8, 17,9 e 16,0, explicitando as contribuições dos fônons para esses valores, e o fator de qualidade, recíproco da perdas dielétricas, 𝑄𝑢×𝑓 ≈ 124,74 e 83 THz, extrapolado para a região de micro-ondas em 10 GHz, para o LCMO, GCMO e YCMO, respectivamente. Medidas de XPS mostraram que os estados de oxidação dos íons de Co e Mn são semelhantes entre si, e principalmente do tipo Co2+/ Mn4+ para todos os sistemas estudados, sendo que para o GCMO, o acoplamento spin-fônon e as perdas dielétricas relativamente maiores indicaram que esse sistema possui elevada desordem estrutural.

Orientadora: Profa. Dra. Marcia Tsuyama Escote / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2017. / Neste trabalho foram estudados os efeitos da substituição do Bi por um elemento terra-rara (R = Pr, Dy) e da adição de polímeros nas propriedades físicas de compostos de BiFeO3 (BFO) sintetizados pelo método hidrotermal assistido por micro-ondas. Inicialmente, amostras de BFO foram preparadas em diferentes condições de síntese (tempo, temperatura e concentração de KOH) e com este estudo escolheu-se os parâmetros de síntese utilizados neste trabalho para síntese de todas as amostras. As sínteses hidrotermais foram realizadas a 200 °C por 120 min com concentração de KOH de 4 M. Os compostos preparados foram avaliados por meio de medidas de difração de raios X (DRX) e de imagens de microscopia eletrônica de varredura (MEV). Na segunda etapa, o efeito da substituição de bismuto (Bi) por praseodímio (Pr) ou disprósio (Dy) foi investigado por meio de medidas das propriedades físicas caracterizadas por medidas de DRX e análise pelo método de refinamento de Rietveld, imagens de MEV, espec-tros de absorção na região UV-Vis, medidas de constante dielétrica em função da frequência e medidas de magnetização em função do campo magnético aplicado (MxH) e da temperatura (MxT). Por meio das análises de DRX das amostras de Bi1-xRxFeO3, foi observado que com a substituição de Bi por R as amostras tendem a cristalizar-se de forma polimórfica, apresentando duas simetrias: uma romboédrica (R3c) e outra monoclínica (Cc), sendo que a proporção da simetria monoclínica tende a aumentar com o aumento de x. Este polimorfismo, em geral, está associado a presença de Fe2+ na estrutura do Bi1-xRxFeO3, que exerce forte influência nas pro-priedades magnéticas destes compostos. As medidas elétricas mostraram uma melhora dos va-lores da constante dielétrica destas amostras quando comparadas a amostras sem substituição e com resultados listados na literatura para compostos BiFeO3 dopados preparados por outras metodologias. Resultados de absorção na região UV-Vis dos compostos Bi1-xRxFeO3 eviden-ciam uma diminuição do gap de energia de 2,1 eV para a amostra com x = 0 a 1,7eV para com x = 0,3 (Pr). Por fim, no estudo do efeito da adição de polímeros ou surfactantes, foram adici-onados os seguintes materiais: polietilenoglicol (PEG), polivinilpirrolidona (PVP), carboxime-tilcelulose de sódio (NaCMC) ou brometo de cetiltrimetilamonio (CTAB) com o objetivo de verificar a influência de diferentes morfologias nas propriedades físicas do BFO. De fato, o surfactante na síntese do BiFeO3 modificou a morfologia destes compostos, sendo que o resul-tado diferencial foi a obtenção do BiFeO3 na forma de nanobastões utilizando o CTAB. Os demais surfactantes apresentaram formatos similares aqueles já descritos na literatura. As me-didas de UV-Vis revelaram que o valor do gap de energia variou de 1,7 a 2,1 eV com a variação da morfologia do BFO, sendo que este resultado já foi observado em compostos de BFO com diferentes morfologias na literatura. As medidas de constante dielétrica em função da frequên-cia apresentaram um comportamento similar àqueles observados para o BFO preparado sem surfactante. As caracterizações magnéticas revelaram modificações nas curvas de MxT e MxH na região de baixa temperatura (<50 K), o que foi atribuído a presença de fases adicionais nestas amostras. / In this work, the effects of chemical substitution and addition of polymers on the physical prop-erties of BiFeO3 (BFO) compounds synthesized by microwave-assisted hydrothermal method were studied. Firstly, samples of BFO were prepared using different synthesis conditions (time, temperature, KOH concentration), with this study we chose the synthesis parameters used in this work to produce all samples. In order to obtain the parameters that allow the production of compounds with the desired crystalline phase. Hydrothermal syntheses were performed at 200°C during 120 min with KOH concentration of 4M. The compounds were evaluated by X-ray diffraction (XRD) measurements and images of Scanning Electronic Microscopy (SEM). In the second step, the effect of bismuth (Bi) substitution by praseodymium (Pr) or dysprosium (Dy) was investigated by measurements of the physical properties characterized by XRD meas-urements, and analysis by the Rietveld method of refinement, SEM images, absorption spectra in the UV-Vis region, dielectric constant measurements as a function of frequency, and mag-netization measurements as a function of the applied magnetic field (MxH) and temperature (MxT). By means of the XRD analysis of Bi1-xRxFeO3 samples, it was observed that with Bi for R substitution these samples are likely to crystallize in a polymorphic way, which present a rhomboedric (R3c) and a monoclinic (Cc) symmetry. The proportion of monoclinic symmetry tends to increase with the increasing of x. In general, such polymorphism is related to the Fe2+ content in the Bi1-xRxFeO3 structure, which provides a strong influence in the magnetic proper-ties of these compounds. Electrical measurements of the samples show dielectric constants val-ues similar to values observed for undopped and dopped-BiFeO3 prepared by other methodologies. UV-vis absorption results of Bi1-xRxFeO3 compounds revealed a decrease of energy gap from 2.1 eV for sample with x =0 to 1.7 eV for x = 0.3 (Pr). Finally, study of the effect of polymers or surfactants addition, the following materials were added: polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (NaCMC) or cetyltrimethylammonium bromide (CTAB) to verify the influence of different morphologies on the physical properties of BFO. In fact, the morphology of BFO was modified through the sur-factant addition, the most remarkable results is the nanostick shape observed for BFO samples prepared with CTAB. Samples prepared using the other surfactants revealed different mor-phology than those reported in literature. UV-vis measurements revealed energy gap varying from 1.7 to 2.1 eV for BFO samples with different morphologies. Dielectric constant measure-ments as function of frequency presents similar behavior than those observed for BFO without surfactant. Magnetic characterizations revealed changes in low temperature region (<50 K), which is attributed to the presence of additional phases in these samples.

Les systèmes multiferroïques magnéto-électriques sont des matériaux multifonctionnels très importants du point de vue des applications dans le domaine de l’électronique ou de la spintronique puisqu’ils présentent simultanément des ordres électriques et magnétiques généralement couplés. Ils peuvent donc répondre à la fois à l’application d’un champ magnétique et d’un champ électrique. L’une des familles de multiferroïques magnéto-électriques les plus étudiées est la série RMn₂O₅ où R est une terre rare. Ma thèse porte sur le rôle de la terre rare sur le caractère multiferroïque et sur les propriétés magnétiques de ces composés. De nombreux travaux ont déjà été publiés mais très peu concernent les composés SmMn₂O₅ et GdMn₂O₅, difficiles à étudier aux neutrons. Pourtant ce sont des composés clés, à la frontière entre des composés à terres rares légères qui ne sont pas multiferroïques et ceux à terres rares lourdes qui le sont. Je me suis donc intéressé à ces composés. Grâce à une étude théorique basée sur une analyse de symétrie et des calculs numériques ab initio tenant compte du fort couplage spin-orbite, nous avons pu prévoir un modèle pour l’ordre magnétique stabilisé dans Sm et Gd. Nous avons en parallèle étudié expérimentalement les structures magnétiques pour ces deux composés par le biais d’une analyse des donnés de diffraction de neutrons sur poudre utilisant des matériaux isotopes de Sm et Gd. Ma thèse a permis d’une part de valider le mécanisme d’échange striction comme origine du couplage magnéto-électrique dans cette série importante de multiferroïques. Elle a permis d’autre part de mettre en évidence l’existence d’une interaction d’échange supplémentaire dans GdMn₂O₅, à l’origine de la forte polarisation électrique dans ce membre de la série. Ces résultats amènent plus de clarté à la compréhension de la multiferroïcité dans ces systèmes. / The magneto-electric multiferroic systems are multifunctional materials very important for applications in the field of electronics or spintronics since they present simultaneously electrical and magnetic orders, which are generally coupled. They can thus respond to both the application of a magnetic field and an electric field. One of the most studied magneto-electric multiferroic families is the RMn₂O₅ series where R is a rare earth. My thesis deals with the role of rare earth on the multiferroic and the magnetic properties of these compounds. Numerous works have already been published, but very few concern the compounds SmMn₂O₅ and GdMn₂O₅, difficult to study with neutrons. Yet these are key compounds, on the border between light rare earth compounds that are not multiferroic and heavy rare earths that are. This explains my interest for these compounds. Using a theoretical study based on a symmetry analysis and numerical calculations ab initio taking into account the strong spin-orbit coupling, we were able to predict a model for the stabilized magnetic order in Sm and Gd. We have experimentally studied the magnetic structures for these two compounds by means of an analysis of the powder neutron diffraction data using Sm and Gd isotopes. On one hand, my thesis allowed to validate the mechanism of exchange striction as origin of the magnetoelectric coupling in this important series of multiferroics. On the other hand, it has made it possible to demonstrate the existence of an additional exchange interaction in GdMn₂O₅, at the origin of the strong electrical polarization in this member of the series. These results provide greater clarity to the understanding of multiferroicity in these systems.

Les matériaux multiferroïques sont des matériaux dans lesquels des ordres magnétiques, électriques et élastiques peuvent coexister dans une même phase. Ces ordres peuvent être couplés entre eux et l’étude de ces couplages permet de mieux comprendre les mécanismes à l’œuvre dans ces matériaux. Cette thèse porte sur l’étude de différents composés multiferroïques par spectroscopie Raman. Dans la ferrite de bismuth (BiFeO₃), l'effet de la contrainte sur le magnétisme, aussi bien sur les films minces (par contrainte épitaxiale) que le bulk (par pression hydrostatique) est étudié en détail. Cette thèse présente également une étude des excitations hybrides magnéto-électriques (électromagnons) dans les composés de type II à forte polarisation ferroélectrique comme CaMn₇O₁₂ et TbMnO₃. En outre, les modes de phonons ainsi que les excitations de basses énergies ont été étudiés (notamment sous champ magnétique) dans des composés au magnétisme frustré comme h-YMnO₃, h-YbMnO₃ et dans le langasite de fer au niobium. / Multiferroics are materials in which magnetic, electric and elastic orders can coexist in the same phase. These orders can be coupled to each other and their study of high interest to understand the mecanisms at stake in the multiferroic materials. This PhD thesis has been focused on the study of several multiferroic compounds by the mean of Raman spectroscopy. In bismuth ferrite (BiFeO₃), the effect of strain on the magnetic order, both on thin films (epitaxial strain) and single crystals (hydrostatic pressure), has been thoroughly investigated. This thesis also focuses on the study of hybrid magneto-electric excitations (electromagnons) in type II multiferroic compounds with strong ferroelectric polarizations such as CaMn₇O₁₂ and TbMnO₃. Furthermore, phonons modes and of low energy excitations have been measured and studied (especially under magnetic field) in compounds with frustrated magnetic orders such as h-YMnO₃, h-YbMnO₃ and in the niobium iron langasite (Ba₃NbFe₃Si₂O₁₄).

Ce travail de thèse porte sur la réalisation de deux instruments adaptés à l’étude de couches minces par spectrométrie Mössbauer du 57Fe par électrons de conversion (CEMS) et à leur utilisation pour la caractérisation de films épitaxiés de ferrite de bismuth BiFeO3 (BFO). Le premier dispositif est constitué d’un compteur proportionnel couplé à un module thermoélectrique. Il permet l’acquisition de manière simple et économique de spectres Mössbauer sur une gamme de température variant de 245 à 375K et sous une induction magnétique externe allant jusqu’à 1,4 T. Un second dispositif a été développé sur la base d’un channeltron™et d’un cryostat à circulation d’hélium pour des acquisitions allant jusqu’à 4 K. Les analyses CEMS ont été réalisées sur des couches minces de différentes épaisseurs de BFO (110) et (001) épitaxiées sur LaAlO3 et SrTiO3. Au-delà d’une épaisseur critique, les couches de BFO (110) présentent un mélange de phases magnétiques colinéaire et cycloïdale. La phase colinéaire présente un axe d’anisotropie suivant [001] dans le plan de la couche et lamodulation cycloïdale se propage dans un plan perpendiculaire à celui-ci. Des effets combinés de contraintes et dimensionnalité ont été avancés pour expliquer la déstabilisation de la cycloïde pour les couches les plus fines. Dans les couches minces de BFO (001) présentant une phase tétragonale de BFO, les mesures CEMS ont montré que la température de mise en ordre magnétique se rapproche de l’ambiante lorsque l’épaisseur des couches diminue. / This work is devoted to the development of two Mössbauer detectors dedicated to thin films studies by conversion electron Mössbauer spectrometry (CEMS), and to their use for the characterization of bismuth ferrite BiFeO3 (BFO) epitaxials thin films. The first designed instrument is composed of a proportional counter and a thermoelectric module. It allows CEMS acquisitions of Mössbauer spectra from 245 to 375K with an external magnetic field upto 1.4 T. The second device is based on a commercial channeltron™ and a continuous flow cryostat allowing measurements downto 4 K. The CEMS measurements have been performed on (110) and (001) oriented BFO layers with various thickness deposited on LaAlO3 et SrTiO3 substrates. Beyond a critical thickness, the (110) BFO exhibits a mixing of collinear and cycloidal magnetic phases. The collinear phase shows an anisotropy axis [001] direction which is located in the sample plane. The cycloid propagation plane have been found to be perpendicular to the sample plane. Both epitaxial strain and size effects have been proposed to explain the cycloid destabilization in the thinner films. In (001) BFO thin films, exhibiting a BFO tetragonal phase, the CEMS measurements have shown that the magnetic ordering temperature tends to decrease with the layer thickness.